Certain para-menthylcyclohexanol ethers of certain glycols



Nov. 13, 1951 M. DE GROOTE ET AL 5 5 CERTAIN PARAMENTHYLCYCLOHEXANOL ETHERS OF CERTAIN GLYCOLS Filed Nov. 1, 1949 MENTHYLCYCLOHEXANOL C l-I 0 I007 |OO% ZZZE/fiii. PETT/NG/LL E A TTORNEY Patented Nov. 13, 195i 1 I D" ST ES :QEBIAIN R BA:MEN YLCXQLQEIEXANOL BS Q flmmmomcots.

' Melvin De Groote, University Gity, and Arthur *F. Wi'rtel and- Ow'en H. Pettingill, Kirkwood, Mo.,

- assignors to Petnolite Corporation, Ltd., Wilmington, Del a corporation of Delaware,

Application November 1, 1919, Serial No. 121,814

The present invention is poncerned with eertairjr new, chemical products, compounds, or com- -which have -useiul application in varioi 'sarts. It includes methods or procedures -for manufacturing said new chemical products, compounds or compositions; as well as the products, compounds or" compositions themselves.

two have discovered that if one treats paramenthyl-cyclohe xanol with propylene oxide and then with ethyleneoXidewv-ithin the proportions hereinafter specified, the mixed menthylcyelohexanol'glycol ether so obtained i an unusually efijective' demulsi-fying agent for water-in-oil emulsions, and also has utility in various other arts hereinafter described- One specific example exemplifying the herein conternplated compounds is the product obtained "by reacting one pound mole ofpara-menthyleyelohexanol with 2-3 pound moles of propylene oxide, followed by reaction pound moles'of :ethylene oxide; Sueh egryalkylationsare usually conductedin the presence or an alkaline'eatalys't. "This specific eompound inst mentioned is only one of a series of siini-lar compounds having, in the main, the same general structure orcompos'ition.

-Previ'ous reference has been made to the -fact that the herein specified products are of -;particular value for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as --cut oil, ---roily oil? ---emulsi -fied oil, etpand which eomprise iine droplets of naturallyoccurring waters or brines dispersed in a more or less permanent" state throughout the oil whiclreonstitutes the continuous phase of 'the emulsion. 7

"This specific application or use of our reagents is described and claimed in our -co-pending applica-tion, Serial No." -1 24,-8-1 3, now'Patent No. '2, 558 ,-511,-.filed November 1, 1949.

"*The compounds*hereindescribedf are not only useful for breaking oil field emulsions, but are useful also for various other purposes, such as -a ."br :k inducer in ithedoctor treatment of sour hydrocarbons, as an "emulsifying -agent,-as a eomponent the preparation of micella-r solu- .5 Claims. (01. 260-611) tions, as an additive to non-hydrocarbon 1ubri cants, as an intermediate for further reaction by; virtue of the terminalhydroxylradical, etc;

It is well known that ;a variety of ;compounds containing a reactive hydroge'n atom, -i. eg, a ay drogen atomattached to oxygen, nitrogen, or sulfur will react with al-kylene oxides, particularly ethylene oxide or propylene oxide, to -yieldthe correspondin lycol or polygl-yo'ol derivative Such oxya'lky-lated derivativesare readily ere-g pared from chemical compounds in which the hydrogen atom is directly'attaehed to oxygen, and particularly in the -ca se; ;o'f alcohols or ph'e -F H01S Sll6hja$ aliphatic alcohols, -pheno1s,alky I- aryl alcohols, alicycl-ic alcohols, phenoxyailkanols, substituted phenoxyalkanols, etc. Generally speaking, it has been found advantageous to react a water-insoluble hydroxylated material, having 8 carbon atoms or more,'-with an alkylene oxide so as to introduce wateresolubility, or at least significant or distinct hydrophile character, with the result that the derivative so obtained ha surface-active properties.

Examples of suitable reaotants' oj this type include octyl alcohol, decyl alcohol, dodecyl alcoho t tradeoyl aleoh l. z ctadeey'l alcohol ui i rhs e trot-u ti t man: @54 1 li henol, ,octylphenol, .nom'lphenol, d" cardano as well as the corresponding alicyclio alcohols ob} tained by'the hydrogenation of the afor'eme 4 tioned Phenols. ,It has been suggested that at least some of such materials be used in the resolution of petroleum emulsions. nsiar as we are aware, none of such' 'materials represent products'which are acceptable ,in fienrulsification today from a competitive standpoint. In the majority of cases such products are apt to be one sixth, one-fifth, one-fourth, .or one-third as good as available demulsifying agents on the same percentage-of-active-material basis or same cost basis. I1; In our co-pending application Serial-"Nd 124,811, now Patent No. 2, 558,j510,-filed November 1,1949, we stated: We have discovered a :very few exceptions t 3 the above general situation. For example, we have discovered, if one treats para-menthylcyclohexanol with ethylene oxid and propylene oxide so as to yield a cogeneric mixture of glycol ethers, that such mixed derivative has unusual properties, provided that the composition lies'within a certain range, as hereinafter specified. A specific exemplification of this range is the product obtained by treating one mole of para-menthylcyclohexanol with 23 moles of propylene oxide, and then with 27 moles of ethylene oxide. Similarly, one may treat the para-menthylcyclohexanol with the 27 moles of ethylene oxide first and then with the 23 moles of propylene oxide next.

In subsequent paragraphs;from;time to time reference i 1 made t'o'f; compounds or cogeneric mixtures. At first glance, it may appear that such language is indefinite, and perhaps, con-1 tradictory. It is the intention at th e momen only to point out that there "is nd'inccnsistehe in such description, and that, subsequently, there will be a complete explanationof-why such. desig nationisentirely proper. M The cogeneric mixtures of glycol. ethers of para-methylcyclohexanol are unusually effective number of oil field emulsions; which, oddly enough, appear rather widely distributed geographically. These para menthylcyclohexanol ether mixtures do not; appear tobe universally competitive, and, as a matter of fact, appear to be highly selective in regard to their action as demulsifying agents, However, such products have significant utility in a number of ,diiferent oil fields where they serve better than any other available demulsifyingagent. Theirutility may, of course, increaseas time goesalong. v

Para methylcyclohexanol is obtained by the hydrogenation of menthylphenol. The procedure is essentiallythe same as employed in the conversion of phenol-to cyclohexanoL; Me t y r phenol has been supplied by the Hercules Powder Co., wilmingtom-pelaware. The formula of r nenthylphenol is believed to be as follows:

. s I Q .CH CH:

CH CH:

"The product obtained by hydrogenation is, of course, the corresponding cyclohexanol, to wit, menthylcyclohexanol, the formulaof which, is asfollows:

The molecular weight of para-menthylcyclohexanol is 232; the commercial product actually shows va molecularweight slightly less.v For con venience, we have taken the molecular weight of the commercial product as 238.,

It is very peculiar that the effectiveness of the demulsifying agents herein described seem to be limited to a very narrow range, or area, as

demulsifying agents lie approximately within a I small and hitherto unsuspected area indicated by .the trapezoid. determined .by the points 8, 9, "110 and 11. More specifically, particularly effective demulsifying agents appear within a smaller range, as set forth approximately by the rea indicated by the segment of a circle in which the areajrof the segment is limited to derivatives; in "which menthylcyclohexanol contributes at least 4% byweightcf the ultimate compound. y The circle itselfiis identified by the fact that the points 1, 3 andfi appear on the circle. The more effective of these better compounds or cogeneric mixtures are those which appear within the triangle which'represents part of the circle 124,811, filed November-,1, "1949.. We havejg and part of the segment, to wit, the triangle identified by the points 1, 3, and 6. The most effective compounds or cogeneric mixtures ofall are those which fall within the inner central triangle :of the larger outertriangleidentified by the points 1, 3 and 6 0 Wit,the smaller triangle identified by the points 2, 4 and 5. .The most outstanding of these effective compounds or cogenerici tures is one which appears to fall substan v at the center of. thesmaller triar gleiden ified .by point 7. This particular point is'obtainedby" treating one moleof para-menthylcyclohexanol with 23.5 moles of propylene oxide,- followedby treatment with 27.5 moles of ethylene pxide fln spite of the uniguecharactenof the 912; pounds previously described we have made addie tionally an invention within an invention, This can be illustrated byreference to the compounds or ,cogeneric mixtures whose composition determined by the inner triangle 2,4, .5. This preferred class of derivatives,-. or, for. that matter; all the herein described products, can be made -in three diiferent ways; (a) by adding propylene oxide first and then ethylene oxide, (l l). by add:- ingethylene oxide first and then propylene oxide; or (c) by adding the two .oxides,at random;,in5 different, or uncontrolled addition so as to produce a polyglycol ether in which the-propylene radicals or ethylene radicals do not appear in continuous succession, but are heterq eneo ly distributed. 1

The present invention representsthe invention '7 within the invention referredto ;in; our;-a fore; mentioned co-pending application, vSerial that 'much more effective demulsifiers ar H bf tained by. adding propylene oxide first an 81;): sequently adding ethylene oxide,otherthan: some other procedure, such as adding ethylene oxide first and then propylene oxide or; a mixed addition. This is particularly true in regard to ithe compositions coming within the segment of, the circle previously referred to in the drawing, For convenience of comparison with our co-pending applicationandalso inorder to emphasize the present invention, i. 3 e., the invention withinfa n n en ienrwe f 931. 1 .eqo tsi bs ant a y. the

of the two, is conventional.

cam-sac example, U. '8. Patent No. l2;440,093 ,'idatedApril 20, 1948, to Israel, and British PatentjNo. 602,591, applied for February 12, 19.45..

:Ewample 1 The reaction vessel employed was a stainless steel autoclave with-jthe usual devices for heating, 1 heat control, stirrer, inlet, outlet, etc... which is conventional in this typeof apparatus. capacity was approximately 40 gallons. The stirrer operated at aspeed ofapproximately250 R. P. M. There were chargedinto the autoclave 23.8 pounds of para-menthylcyclohexanol. There were then added one pound 3 ounces (approximately 5% by weight) ofground caustic soda. The autoclavejwa's sealed, swept with nitrogen gas, and stirring started immediately and 'heat "a plied, and the temperature allowed to --rise to approximately-150 C.- At' this point addition df propylene oxide was started. It was-added cont'iiiuousl y atsuch speed that it was absorbedby the reaction as rapidly asadded. The amount of propylene oxide added'was -l36pounds. The time igeduh'ed to'add this propylene-oxide was slightly i r-excess-of one hour, about l hours. During this time the temperature was maintained at 515? to-l* 6O C., using cooling water through-the 'coils when necessary and otherwiseapplyheatif required. At the end-of the addition propylene oxide there was added etl-ryleneoxide, as previously indicated. The amount of ethylene oxide addedwas 1205 pounds. ;The temature employed; and operating conditions, the same as-withthe addition o'f propylenfi to be noted, however, that-ethylene oxideappe'ars 'tofbe-more reactive and the reactionseems torequire a greater amount of cool-- igiawa'ter to holdthe temperature range as' indie e d. The time required to add the ethylene e was about the same, orslightly less, usually a little more than an hour. p iDur'ing the addition of the'oxidesfthe "pressure was held at approximately 50 "pounds perflsqua're gauge pressure, orless. When'all theox-ide hhdbeen added "(ethyleneoxide being-the final addition in this particular instance) the auto-- c1 e wagpermitteuft stay at --the-s'ame"temstantially the total weight of the initial react-ants? preceding.

if, The .same ,procedurewas followedas -;ample 1, except that a mixture, to wit,. .526 1 pounds "of propylene o ide and ethylene oxide,

5 simultaneously.

Ewam lgpz.

The same procedure was followed as in Example 1, preceding, except that the order of addition of the oxides was reversed, the ethylene oxide beingadded first and the propylene oxide last.

The time period, temperature range, pressure, etc., were kept the same as in Example 1,

Example .3

were added over a 2-hour period. This mixture" of ethylene oxide and propylene oxide was 010-; tamed-from c136 pounds of propylene oxideand 130.5 ptijundsof ethylene oxide. In this instance ,again' the time range,'--temperature and pressure; I were kept substantiallythe same as in Example" 1;; fpreceding.

Example 4 Thers'ame, procedure was followed as in Ex,- ample .1, on a laboratory scale, employing a small autoclave having a capacity of approximately ,one 1iter,.up to a ,5- ga1lon size. The amount unparamen y qy lg exano mplqyedwas 21. 1.; "ms.- the amountof propylene oxide employed was2'12 grams, and the amount of ethylene oxide Ier'nkployed was24l grams. The 'amount'ormusus soda employed 2.4 grains. The operatingcon dit' were substantially .the same asion .a larger e.- Actually, the reaction seemed to go faster he small autoclave .and the time of absorption bereduced, if desired. ,-In'many,instance' s, ab ption would take place in the'laborato fii autoclave in a fraction of the time .requ'iredin the larger autoclave; in fact, in manyfinstances, absorption was complete in 5 to 1'0 or 15 Iminutesas cgmpared toone hour on a larger scale. Needless to saw onalarge scale, addition must be con ducted car because there is an obvious hazard in handling a .large guantity of material an -autoclave which is not .:necessarily present inathe useofa small-vessel.

The sa n e procedure was followed as in Exampiei; preceding, in every respect, except the variation-described in Example 2, preceding, 1. e., the ethylene'oxide, was added first and the pro pylene foxide added last.

Example '6 The same procedure was followed as in Example '4 in' every instance, except the modificatio'n previously described in Example 3, to wit, the propylene oxide and the ethylene oxide, were mixed together and added "in approximately 15 minutes to one-half hour. In all other respects the procedure was identical with that described in Example 4.

The following table includes a series of compounds or cogeneric mixtures which have 'been selected as exemplifying the herein included products. Types of herein noted compounds ,or cogeneric mixtures have been .produced in three different ways: (a) first adding the propylene oxide and then the ethylene oxide; (1)) first add-' ing the ethylene oxide and then the propylene oxide; and (c) mixing'the ethyleneoxide'and the propylene oxide all together andadding them The data are summarized in the following table;

I Pointon' e gt: tPie; V j 1gb. I P er I VCVt. flex gran}: Wt. Used Molal 2 WtiUsed Molal Wt.'Used Molal V Ex. No. Final Final Final tying in Grams llatio Glycol in Grams Ratio Glycol in Grams Ratio Glycol s cum 7 Ether Ether Ether lycol Ether 238 1.0 15. 715 12. 32 45 v 635 14. 43 40 1' 238 1. 0 10. 0 1, 192 20.55 50 953- 21.65 40 2 238 1. 0 5. 0 2, 620 45. 55 1, 910 43. 3 e 3 238 1. 0 10. 0 1, 071 18. 50 1,071 24. 38 45 4 238 1. 0 5; 0 2, 382' 41, 1 2, 140 48. 6 45 5 238 1. 0 5. 0 2, 145 37. 0 45 2, 380 54. 2 50 6 1 238 1. 0 8.5 1, 360 23. 42 48. 5 1, 205 27. 4 43 7 238 1. 0 9. 2 1, 258 21. 64 48. 6 1, 092 24. 82 42. 2 (1) I 238 1. 0 9.0 1, 255 21. 62 47. 4 1, 154 26. 2 43. 6 (1) 238 1.0 8. 8 1, 248 21. 5 46. 2 1, 218 27. 65 45. 0 (1) 23s 1. 0 Y a. s 1, 356 :23. as 49. o 1, 202 t 27. a 43. 4 1) 238- 1.0 8. 5 v 1, 360 23. 42 48. 5 '1, 205 27. 4 43. 0' v 7 238 1. 0 8. 4 1. 321 22. 48. 6 1, 275 29. 0 45.0 (1) 238 1. 0 8. 2 t 1, 438 I 24. 75 49. 5 1, 230 27. '42. 3 1 238 1. 0 8. 0 1, 444 24. 86 48. 5 1, 295 29. 4 43. 5 (1) 238 1. 0 7. 8 1, 446 24. 90 47. 4 1, 370 31. 15 44. 8 238 1. 0 7. 0 1, 668' 28. 72. 49. 0 1, 496 33. 05 44. 0 51) 238 1. 0 6. 0 1, 965' 33. 90 49. 5 1, 766 40. 2 44. 5 1) 238 1. 0 20. 0 309 5. 33 26. 0 643 14. 6 54.0 8 238 1. 0 4. 0 1, 548 26:7 26. 0 4, t 94. 7 70. 0 i 9 238 1.0 4.0 4, 520 77. 8 76. 0 1, 27. 0 20. 0 10 238 1.0 I 20. 0 '714 12. 3 50. 0 238 5. 42 20. 0 11 I I Within inner triangular area. Duplicated for convenience. In'the preparation of the above compounds the alkaline catalyst used was either flake caustic soda finely ground withmortar and pestle, or powdered sodium methylate, equivalent to 5% by weight of the para -menthylcyciohexanol which was employed.

Indicates limits of trapezoidal area.

For reasons which are pointed out hereinafter in greater detail, it is substantially impossible to use conventional methods and obtain a single glycol ether of the kind described. Actually, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known method without decomposition. The properties 'of'such a mixture represent the contribution of the various individual members of the mixture.

Although one cannot draw a single formula- ROI-I can represent para-menthylcyclohexanol,

R0 is the ether radical obtained from para-i menthylcyclohexanol by removal of the hydrogen atom attached to the oxygen atom.

If one selects any hydroxylatedcompound and subjects such compound to oxyalkylation, such;

for sake of convenience, may be indicated as; RO(C2H4O)30H. Instead, one obtains a cogeneric mixture of closely related homologues in which the formula may be shown as the following; RO(C2H4O) H, wherein n, as far as the statistical average goes, is 30, but the individual members,

present in significant amount may vary from'instances where-n has a value of 25 and perhaps" less, to a point where u may represent'35 or more. Such mixture is, as stated, a cogeneric;

, closely related series of touching, homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention 'is directed tolth'e article entitled Fundamental Principles of Condensation Polymerization, by Paul J'. Floris which appeared in Chemical Reviews, volume 39'}; No.1,page137. v

Unfortunately, as has been pointed out by F1 ry; and other investigators, there is no satisfactory. method, based on either experimental or math- T ematical examination, of indicating the exact; proportion of the various members of touching homologous series which appear in cogeneric'condensation products of thekind described; This means that from the practical standpoint, 1b., the ability to describeshow to make the product; under consideration and how to repeat such pro duction time after time without diflicultyfit necessary to resort tov some other method. of def. scription. M -I 519 Actually; fromiaipracticahstandpoint, its; much more .satisfactory perhaps, to describe the ulti# mate composition termstof the reactants, i. of, menthylcyclohexanolandtheltwo alkylene oxides. llheereason. for statement is. the following: Iii-one; selects azspecific: compound; it must be borne; lnrmind'thatsuch compound is specific insofar thattlieiacogeneric mixture in terms ofizstatisticak average will conform to. this formu- .la.'.-" .1'his may be; illustrated by-an. example such as; ROiGai-IQimiEaHsOlzrI-I. If one. combines the: reactants in the" predetermined weight ."ratio soiasto: give theoretically this specific component and assuming only one chemical compound were termed; what happensv isz'that, although thisfipan :tion-lar compound may be. present in a. significant amount probably: less than 50%, actually, one obtains a cogeneric: mixture of touching .homologues'm which the-statistical averagedoes correspond to' this. formula. For instance, select;- ingzxeactants, which, at least theoretically, could givethersinglelcompound V RQ(C3.HU)23(C2H40) 27H what-actually happens is: that one obtains,- a sort oiidouhla coaenerio mixture,v for the reason that in each batch or continuous additionof. alkylene oxide, a-cogeneric; mixture-is formed. Since the present; products. requiretheaddition of at least two, different multirmolar proportions of each of tmrdifierent; alkyleneoxides, (ethylene oxide and propylene.- oxide) itbecomes-obvious thata rathercomplex cogenericmixture must result,

{Ighis canbe bcstgillustrated by ex ample. Assume thahoneyisrgping, to. use the ind-icatedrratio, towit, one v pound mole of menthylcyclohexanol, 23 pounds of propylene oxide and 27 pounds of .ethylene oxide, The initial step involves the treatmentct one pound mole. of menthylcyclohexane with- 23 pound moles of propylene oxide SQ: as toyield: theoretically R (C3HsO)-23H; actually, as pointed: out, .onedoes not obtain ROTCBHGO.) "H

miwnicn 1t 18! 23, but: one obtains a; cogeneric mixture, in which there are present significant amounts of homologues, in which n varies irom idi ll and- 12on up t0 35., 35' possibly 40 or beyond. Astatistical average, however, must,'-o

course, correspond to the proportion of theinitial reactants, i. e., a, compound of the formula RO(C3H6O)23H, which is present undoubtedly to a signiflcant extent. i

' When this-cogenericmixture is then subjectedtoreaction with- 27- moles of ethyleneoxide, it

aoccaneoin-rczmonir which, as previously-pointed out, components present, in; important percentages are. those in ditch could: vary anywhere from 10. or higher, uptoB-d 6:40. By: the; same token, components present in. important percentages arethose in whichin' could var -anywhere from mar. 14, and

possiblyeven less; npztn 46,341,. 42,43 or 45.2 In deed; h'omoiogues of 1a: lower or. avhiigher valu'e of mandala" be: presentin minor amounts,- the components: decreasing; the

. 1o further removed they are from the average com:- position However, in spite of'such variation in regard to the cogeneric' mixture, the ultimate composition, based on the ingredients which enter into it and based on the statistical average of such constituents, can still be expresse'd by the formula: R0(CrrHeOlzaiQHrOizqH. actual product: exists to some degree in the. .cogeneric. mixturebut it should be looked upon as a statistical. average formula,'rather than the structure of a single or predominant compound in the mixture. w

A' second reason for employing 'areactionmix- .tureto describe the product, is the fact that the molal proportions needinotrepresent'wholemem hers. Wer'have. justapointed-outlthat if. one selects molazl proportions corresponding'tcx 1 RO(C3HeQ).2a(CgH4O)z'iHi then the constituents are added in actual molar proportions; based on whole numbers. If; 10w? ever; one selects a point in the inner triangular area, which, when recalculatedin termsof molar proportions, produces a fractionalnumbengthere' is still no reason' why such proportion ofjiiiitiafl reactant should not be adopted. For instance; one might select a point. in the triangular graph; which, when calculatedin terms of molecular proportions, represents a formula', "such'as1 the following: R0 CaHeQ) 22.51 ammo-an; This; of course, would be inimateria'ljjfor the reason that iiion'estarts' with a; pound mole of menthylcyclo hexanol' and adds 23.15 pound .inoles of propylene oxide, one will obtain, 'onfthe average a mixture closely comparable to the one 'Jrcvious'ly de-; scribed, usingexactly-23; poundl moles otpropylcne oxide instead of 2335. ,Su'cl"1j mixture corresponds to the'compound RO('CI-IeO)2'a.sH' only in the sense of the average statistical value, but not" in the sense that there actually can be a compound corresponding to; such formula. Further discus? s'ion of this factor appears. unnecessary in light. o'rwhat. has beensaid'previously.

Such mixture could, of course; betreated with 27 pound moles of ethylene. oxide. Actually, all that has. been said sums up to this, and that is. that the most satisfactory way; as hasbeen salfd. before, of indicating actual materials obtained by theusual and conventional oxyalkylation process; is in terms of. the initialreactants, and it i's'ojb'- vious that any particular pointonthe triangular graph from a practical aspect, invariably and'iuevitably represents the statistical" average of several or possibly a dozen'or" more closelyrelated cogeners, of almost the same 'compositiombut rep;- resenting a series of touching homo'logu'es. The particular: point selected represents at least the composition of themi'xture expressed empirically in the terms of a compound representing the statistical average.

' Previous. reference has been made to the. fact that comparatively few oxyalkylat'ed' derivatives Ofsimple, hydroxyla'ted cOmDQHnds' findjutility'in actual demulsificati'on practice. We'have pointed outthat we have found a very few exceptions to.

:11 paramentylcyclohexanol contributes; less than 1.0% of the molecular weight. As a matter of fact, in other comparable compounds the paramenthylcyclohexanol may contribute as little as 4% or 75% and yet these particular compounds are efiective demulsifiers. Under such circumstances, it would seem reasonable to expect that some other, or almost any other, substituted cy'clic 6-carbon atom compound comparable to parar-menthylcyclohexanol, would. yield derivaat'ivesequally effective; Actually, this is not the case. We know of no theory or explanation'tto suggest this highly specific nature or action of the compound or cogeneric mixture derived from paraementhylcyclohexanol.

, Referring t'o an examination of the previous list of 32 compounds, it is to be noted that in certain examples, for instance, Examples 9 to 15, inclusive, all'thepropylene-oxideis added first and then the ethylene oxide is added. Compounds indicated by Examples 1 to 8 are substan tially the same, as far as composition goes, but are reversed, insofar that the'ethylene oxide is added first and then the propylene oxide. Other compounds having substantially the same ultimate composition, or at least, very closely related ultimate compositions, having a furthervariation in the distribution of the'propylene oxide and ethylene oxide, are exemplified by Formulae 16 to32,inclusive.

As has been pointed out previously, for some reason which we do not understand, and for which we have not been able to offer any satisfactor theory, We have found that thebest compounds, or, more properly, cogeneric mixtures, are obtained when all the propylene oxide is addedfirst and then all the ,ethylene oxide is added. Although this is true to at least some extent in regard to'all compositionswithin the trapezoidal area in the triangular graph, yet it is particularly true if the composition comes within the segment of the circle previously referred to in the drawing. In such event, one obtains a much more effective demulsifier than by.

any other combination employing ethylene oxide alone, propylene'oxide alone, or any variation in the mixture of the two, as illustrated by other formulae. In fact, the compound, or cogener ic mixture so obtained, as far as demulsification is concerned, is not infrequently at least one-third better than any other derivative obtained in the manner described involving any of the other above variations. 1

The significance of whatv has been saidpreviously becomes more emphatic whenone realizes that, in essence, we have found that one isomer is a more effective demulsifyingagent than another isomer. The word isomer islnot exactly right, although it is descriptive for the purpose intended insofar that we are not concerned with a single compound, but. with a cogeneric mixture, which, in its statistical avera e, corresponds to such compound. Stated another Way, if We start, with one pound mole of menthylcyclohexanol, 23 pound moles of propylene oxide and 27 pound moles of ethylene oxide, we can prepare two different cogeneric mixtures; which, on a statistical average, correspond to the following:

'jlhere is nothing we know which would suggest claimed in our'fco-pending applications Serial that th'e'latter be a much-more effective denlulsi fying agentthan the formerand also that 'it' be more effective for other industrialp'urposes, The applicants have had wide; experience 'with'a wide variety'of surface-active agents, but they are awareof any other similar situationj'withth exception of-a few instances .which are/the sub ject-matter of other, co-pending applications or under investigation. This feature represents'zthe invention within an'inventionpreviously referred to, and, thus, becomes the specific subject-matter Nos."124,8l1 and 124,812, both filed: November I,

, H g V Reference has been made to -the productherein specified; andparticularly for use as'*a"demulsifier; represents a cogeneric mixture of closely related'homologuea This does not mean, that one could not use combinations of such coge'neric-mixturesi For instance, 'in'the previous table, datahave 'beengiven for preparation of cogeneric mixtures which statistically correspond, respectively,-=-to points-L1 3 andS. Such three cogeneric mixtures could be combined in 1 equal weights so asto give a combination in which the mixed statistical average would 'cor-respond closelytopoint'li a We need not add that instead of subjecting menthylcyclohexanol alone to oxyethylation, and oxypropylation, or inversely, oxypropylati'on and oxyethylation, or a simultaneous treatment of both oxides; one can" employ a mixture of menth'ylcyclohexanol along with some' other de sired reactant, such as" alpha-terpineol. For a number of reasons, it is ordinarily desirable=to I use a procedure in which only one product is re? acted at atime.

' Previous reference has been made to the fact that the herein described products orcompounds have utility in fields other than demulsifi-cationl Since these products contain a terminal-'hydroxyli, 1 they can, of course, be used as 'a source of new derivatives by reaction with acids, other oxides such as phenyl ethylene oxide (styrene oxide'ly,

and the like. Such acids-imay'be monoicarboxy or polycarboxy, such as phthalic anhydride. The l products may be} used asassistants informing emulsions, proach micellar' solutions,

An example of such emulsion is the following: r

Emulsion Example A V Grams In the preparation of theabove emulsion the sodium carbonateis dissolved in the water and then the sodium oleate dissolved completely. After this mixture has been prepared, the prod-- not of Example 1 is then added and mixed until the mass is entirely homogeneous.- Then the kerosene is added slowly with constant stirring until a completely smooth emulsion is produced;

7 We also desire to point out that very effective demulsifying agents and emulsifying agents 'can' be obtained from compounds of the kind described by enhancing their watersolubility by the introduction of a sulfo group." For instance, two- 7 moles .of any of the described derivatives can be reacted with one mole of maleic anhydride so as togive the complete ester. can then be treated in the conventional manner particularly emulsions, which ap- This complete ester 1'3 with sodium bisulfita so as to" give the corre spending. sodium sulfo-succinate in the form of a sodium'salt.

What has been said in regard to these com- .p'oundslas demulsifiers also applies in regarcl'to the-zuserosthe compounds for other purposes, to mt emulsifiers sbreak inducers, etc. Inother words, adding the propyleneoxide firstand their thecethylene oxide gives compounds whichxare Superior for various industrial. purposes, and this istrue'particularly when the composition of the compound is within the area designated bythe segment ofthe circle in the drawing.

=r'e-llhroughout the specification elsewhera'refererrce has been made to homologues. It is quite likelythatitwoul'd be equally proper in numerous instanceaiand perhaps all the herein described H products, to refer-to isomers aswell as homolo'guesi zlihe reason for this statement is that propylene oxide; as differentiated from ethylene can, :at least theoretically, combine with a hydroxylated material'ROH to give two difierent derivatives, onev :beirrgv :a. primary alcohol and the ethane-secondary alcohol. This is illustrated by the'followixig:

QLEIsewhere in the specification the word .f,1some1 has been used thus: isomer. It is not fili'eved there is any confusion between such terminology in that particular instance and what said immediately preceding- Attention isv directed to the. fact that the herein described compounds, compositions and the like which, are particularly adapted for use as demulsifiers. for water-in-oil' emulsions, as found the petroleum industry, are hydroxylated derivatives, i.- e, carry or include a terminal hydroxyl radical as part of their structure. We

havefound. that if such hydroxylated compound 91-, compounds 'are'reacted further so as to produce entirely new derivativeasuch new derivatime have the. properties of the original hydroxyla'ted rcompounidnsofar that they are effective bisulfite to'yie'lda sulfosuccinate; Sulfo groups ba'nbe introduced also by means of a 'sulfating a previously suggested, or by treating'the cl ficroaceticacid resultant with sodium stllfite. j However, the class of derivatives most readily earboxy and polycarboxy acids.

' assuming a typical-derivative which can bein- 'dicated thus:

,Such hydroxylatedcompounds can be treated prepare-d wide variety are the estersof monothe ester of the monocarboxy-acid is as follows:

o Ro .0,Hto),.'(o,mo),.'dR The acid ester of a dicarboxy acid is as follows;

The chloroacetic acid ester is as follows:

I o R0(CizlltmnwaHr-o)#3011101 The quaternary compound obtained by reacting the above-mentioned product with pyridine is as follows koroimo) .(otmont CH2? Among the various kinds of monocarboxy acids suitable for preparation of esters, are the alpha: halogen monocarboxylic acids having not over 6 carbon atoms. Typical acids exemplifying this class are chloroacetic acid, dichloroacetic acid, bromoacetic acid, alpha-bromobutyric acid, etc. Needless to say, in this in'stancaand all others where reference is 'made to the acid, the functional equivalent such as the acylchloride, the anhydride. the ester, the amide, etc., may be employed.

Another clas of esters are those obtained from certain drastically-oxidized hydroxyacetylated castor oil fatty acids. The drastically-oxidized acetylated ricinoleic acid compounds are employed to furnish the acyl radical of the ester. In this particular instance, as in allotherinstances, one may prepare either a total ester or a partial ester, and when carboxy acids are employed, one may have not only partial esters which have residual 'hydroxyl radicals or residual carboxyl radicals, but also partial esters in which both are present.

A somewhat'similar type of ester is obtained from hydroxyacetylated drastically oxidized castor oil fatty acids. It is to be pointed out that hydroxyacetylation may take place first, and drastic oxidation subsequently, or the reverse may" be true, or both procedures may be conducted simultaneously. Inany event, such products supply acyl radicals of one type of ester herein included.

Anothersomewhat similar class are esters obtained from hydroxyacetylated drastically-omdized dehydrated ric'inoleic acid. In this class r'icinole'ic acid, castor oil, or the like, is subjected to dehydration as an initial step. Such products may be employed to supply the acylradical of one type of ester herein included.

Another type of ester which may be employed is a sulfo-fatty acid ester, in which there is present at least 8' and not more than 22' carbon atomsin the fatty acid radical. The sulfo radical includes'both the-acidsulfonates and the soltonieacids. Briefly'stated, suitable'sulfo acids herein employed as reactants are sul'fo'olei'o, sul'i-"o r-icinoleic sulfo aromatic fatty acids obj-- tained, for eirar n'plc; from" benzene, toluene,

xylene, etcg andoleic acid or some other un'- saturated acid.

Another class of acids arepolycarboxy acids, such as commonly used in forming plasticizers, polyester'resins, etc. One may use a' tricarboxy acid, such as tricarballylic acid, or citric acid, but our preference is to employ a dicharboxy acid, or

- acid anhydride, such as 'oxalic'acid, maleic acid,

our preference to use phthalic anhydride, maleic anhydride, citraco'nic anhydride, diglycollic acid, adipic acid and certain other acids in the same price range which are both cheap and heatresistant. One may also use'adduct acids of the diene or Clocker type.

Another class of esters are derived from certain high molal monocarboxy acids. It is well known that certain, monocarboxy, organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by thefact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula R..COOH. Certain derivatives of detergent-forming acids-react with alkali to produce soapor soap-like materials and are the obvious equivalent of the unchanged or unmodified detergent-forming acids. For instance, instead of fatty acids one might employ the chlorinated fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominatednaphthenic acids, etc.

The fatty acids are of the type commonly re: ferred to as higher fatty acids; and, of course, this is also'truein regard to derivativ es of the kind indicated, insofar that such derivatives are obtained from higher fattyacids'. The petro leum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, paraflin, etc. Such acids-may have as many as 32 carbon atoms. For instance, see U. .8. Patent No. 2,242,837, dated MayZO, 1941., toshie'lds. V flThe monocarboxy detergent-forming esters of the oxyalkylated derivatives herein described, are preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include oleic acid, ricinoleic acid, linoleic acid, etc. One may employ mixed. fatty acids, as, for example, the 'fatty acids .obtained from hydrolysis of cottonseed oil, soyabean oil, etc. It is our ultimate preference that the esters of the. kind herein contemplated be derived from unsaturated fatty acids, and more especially, 1111- saturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids whichhave been subjected to oxidation. In addition to synthetic carboxy acids obtained by the oxidation; of paraffins or the like, there is the somewhat analogous class obtained by treating carbon dioxide or car;- bonmonoxide, in the presence of hydrogen or an olefine, with steam, or by causing a halogenated hydrocarbon to react with potassium cyanide and saponifying the product obtained. Such products or nixtures thereof, having at least 8 and1not more-than 32 'carb'onatomaand havingat least one carboxyl group or the equivalentthereofgare suitable as acids; and another analogous class equally suitabl'exis'the mixture of carboxylic acids obtained by the alkali treatment of alcohols ofhigh molec' f ular weight formed in the catalytic. hydrogen'a tion of carbon monoxide. One may have esters derived also from more. thanone class, i. e., one may employ mixed esterssuch as esters obtainedpfor example, from high. molal detergent-forming acidshaving 8 to 22carbon' atoms, as previously 7 described, in combination with acids of the alphahalogen carboxy type having less than 8.= carbon atoms, such as chloroacetic acid, bromoacetic acid, etc., aspreviously. described.= .Drastically-oxidized oil, such as drasticallyoxidized castor oil, or drastically-oxidized dehye drated castor'oil, may be employed to supplythe acyl radical. In other instances, one may produce mixed :esters by using polycarboxy acids, such acid As"to this1 particular product, see IT. IS,

Patent No'. 2,34.7,562, dated lipril 25,1944, t4? 7 as phthalic acid, diglycollic acid, etc;, in combine;- tion with detergent-forming acids,.such asoleic acid, stearic acid,,naphthen ic acid, etc..

other caiboxy idsmay b emplo ed in which.

there is also a sulfo'group present, such as sulfophthalic, sulfa-benzoic, sulfo-succinic, etc. Esters may be obtained, from low molal hydroxylated acids having less than 8 carbon atoms, such as hydroxyacetic acid, lactic acid, etc. Similarly,

one may employ low molal aliphatic acids having less than}; carbon atoms,such as acetic acid, butyric acid, etc. 1 Similarly, onemay employ low acrylic acid, methacrylic acid, crotonic acid,fetc} It will be noted that these acids contain various numbers of acyl radicals varying generally up to e 22 carbon atoms for the monocarboxy acids, and as many as 36'carbon atoms in the case of certain polycarboxy acids, particularly the dimerpob tained by the dimerization of 9,1l-octadecadienic J ohnston.

Other suitable acids'are cyclic monocarboxy I V acidshaving not over- 32 carbon atoms. Exam;

plesof such acids include cyclohexaneacetic acid, cyclohexane butyric acid, cyclohexane propionic acid, cyclohexane caproic acid, benzoic acid, 'salij cylic acid, phenoxy acetic acid, etc.

,7 The preparation ofsuch ,esters are conven;

tional and do not require elaborate, description. Generally speaking, our procedure is to react the appropriate amount of a selected hydroxylated f compound with. the free .acid'in presence of a' The triangulaf'graph represents the componentsystem. Using 4 reactantsfi. e. three depicted in the triangular graph, plus 813':

cide, gives a'four reactant system which yields derivatives for demulsification of water-in-oil emulsions, at least-equal to those, herein: scribed. The use-of glycide in a four-component reactant permits unusual structure, as, for ex;

ample, a variety of furcation. Thus, the hydrox ylated initial reactant can be treated, with glycide detergent-forming monocarboxy.

not only Y single class of acids of the kind described,-.but

molala'cids having the vinyl radical, suchfas The time, required is usually in the conventional manner, using an alkaline catalyst, and after an introduction of a molefor-mole ratio of glycide, then propylene oxide can be introduced in the manner previously described, and thereafter ethylene oxide can be added. If desired, the propylene oxide can be introduced first and then one mole of glycide added, followed by ethylene oxide, or both procedures can be employed.

Moreover, glycide can be used to replace a substantial part or greater part of the ethylene oxide, or propylene oxide, or both. Such compounds can be converted into various derivatives of the kind previously described. Under such circumstances, reaction with glycide and an end reactant to supply a terminal radical is not considered as forming a derivative, but as simply forming the end material. The ester and similar derivatives so obtained from the four-component original system, i. e., the one including glycide, are also very effective for demulsification of water-in-oil emulsions, as found in the oil industry.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the segment of the circle in the accompanying drawing in which the minimum para.menthylcyclohexanol content is at least 4% and which circle is identified by the fact that points I, 3 and 6 lie on its circumference, and with the proviso that the paramenthylcyclohexanol be reacted first with all the propylene oxide and then with the ethylene oxide.

2. A cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points I, 3 .and 5, and with the proviso that the para-menthylcyclohexanol be reacted first with all the propylene oxide and then with the ethylene oxide.

3. A cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points 2, 4 and 5, and with the proviso that the para-menthylcyclohexanol be reacted first with all the propylene oxide and then with the ethylene oxide.

4. A cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately at point i in accompanying Figure 1, and with the proviso that the para-menthylcyclohexanol be reacted first with all the propylene oxide and then with the ethylene oxide.

5. A single cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately at point 7 in the accompanying drawing, and with the proviso that the para-menthylcyclohexanol be reacted first with all the propylene oxide and then with the ethylene oxide.

MELVIN DE GROOTE. ARTHUR F. WIRTEL. OWEN H. PETTINGILL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,976,677 Wittwer Oct. 9, 1934 2,176,834 Bruson Oct. 17, 1939 2,213,477 Steindorff et al. Sept. 3, 1940 2,425,755 Roberts et a1 Aug. 19, 1947 2,425,845 Toussaint et al Aug. 19, 1947 

1. A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF PARA-MENTHYLCYCLOHEXANOL; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM PARA-METHYLCYCLOHEXANOL, ETHYLENE OXIDE AND PROPLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATE IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE SEGMENT OF THE CIRLCE IN THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM PARA-METHYLCYCLOHEXANOL CONTENT IS AT LEAST 4% AND WHICH CIRCLE IS IDENTIFIED BY THE FACT THAT POINTS 1, 3 AND 6 LIE ON ITS CIRCUMFERENCE, AND WITH THE PROVISO THAT THE PARAMENTHYLCYCLOHEXANOL BE REACTED FIRST WITH ALL THE PROPYLENE OXIDE AND THEN WITH THE ETHYLENE OXIDE. 